JPH0273819A - Production of polyphenol - Google Patents

Abstract

PURPOSE:To obtain the subject resin having practical softening temperature and useful as a raw material for epoxy resin for sealant and lamination material by reacting an aromatic dialdehyde with phenols at a specific ratio in the presence of an acid catalyst. CONSTITUTION:The objective compound of formula (R is H, halogen or 1-4C alkyl; n is >=0 provided that the component corresponding to n=0 accounts for 30-90% of the whole composition) is produced by carrying out dehydrative condensation of (A) 1mol of an aromatic dialdehyde (e.g. o-phthalaldehyde) and (B) 5-32mol of phenols in the presence of an acid catalyst (e.g. hydrochloric acid or p-toluenesulfonic acid) preferably at 80-160 deg.C for 1-10hr and removing excess phenols from the system by distillation. The amount of the acid catalyst is preferably 0.2-5pts.wt. per 100pts.wt. of the aromatic dialdehyde.

Description

Detailed Description of the Invention [Industrial Application] The present invention relates to a method for producing a phenolic resin for use as an epoxy resin raw material and as an epoxy resin curing agent, which has excellent heat resistance and is useful as a sealing material and a laminated material. .

[Conventional technology]

Conventionally, in the production method of novolac type phenolic resin, formaldehyde is added in an amount of 0.5 to 0.0% per mole of phenol.
It is obtained by carrying out a reaction with an acidic catalyst such as hydrochloric acid or oxalic acid in a range of 9 mol, followed by dehydration and concentration. In recent years, the development of electronic components has been remarkable, and high-density devices such as LSI,
The high degree of integration is remarkable, and higher heat resistance is now required for sealing materials. Therefore, polyphenol (a raw material for tetrafunctional epoxy resin using aromatic dialdehyde instead of formaldehyde)
JP-A-55-139373) has been proposed.

[Problem to be solved by the invention]

However, the polyphenol has a very high melting point due to its single structure, and is not practical for use as a sealing material.

The present invention was made in order to obtain polyphenols having a practical softening temperature.

[Means to solve the problem]

The present invention provides a method for obtaining a polyphenol that solves the above problems by reacting 5 to 32 moles of phenols per mole of aromatic dialdehyde in the presence of an acid catalyst.

(Aromatic dialdehyde) The aromatic dialdehyde used in the present invention is 0-fucuraldehyde, isophthalaldehyde and terephthalaldehyde.

(Phenol) The phenols used in the present invention include phenol, 0-cresol, m-cresol, p-cresol, p-cresol, and p-cresol.
Examples include -5ec-butylphenol, pter t-butylphenol, chlorophenols, and bromophenols.

(Acid Catalyst) Examples of the acid catalyst used in the present invention include hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, oxalic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, etc. .

(Reaction method) Polyphenols are produced by adding 5 to 32 moles of phenols, preferably 6 to 32 moles, of phenols per 1 mole of aromatic dialdehyde.
The acid catalyst is mixed with an aromatic dialdehyde in the range of 25 moles.
0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight.
Add 2 to 5 parts by weight and add 1 to 5 parts by weight in a temperature range of 80 to 160°C.
Polyphenols are obtained by performing dehydration condensation for 10 hours and distilling off excess phenols.

If the amount of phenol is less than 5 moles per mole of aromatic dialdehyde, the proportion of pentanuclear bodies with n=0 in formula (III) below will be less than 30%, and the softening temperature of the resulting polyphenol will be lower than 200°C. exceed.

Moreover, when the amount exceeds 32 moles, the proportion of n=Q exceeds 90% and crystallization occurs, so the softening temperature of the polyphenol increases to 200°C.
This is not preferable.

Furthermore, if the reaction temperature is too low, the reaction will be difficult to proceed, and if the reaction temperature is too high, the amount of high molecular weight will increase and the softening temperature will become high, which is not preferable.

(Polyphenol) The polyphenol obtained by the method of the present invention is as follows-
It is represented by (I[I), (I[) [wherein R is a hydrogen atom, a halogen atom, or a carbon number 1]
~4 alkyl group, n is an integer of 0 or 1 or more, and n=o is in the range of 30 to 90% of the total composition. ] Its softening temperature is in the range of 80 to 200°C. If the softening temperature is less than 80°C, a blocking phenomenon occurs at room temperature, making it difficult to handle. Further, if the temperature exceeds 200°C, it is not practical as a raw material phenolic resin for epoxy resin.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 1.656 g of phenol, 147.5 g of terephthalaldehyde (phenol/terephthalaldehyde = 16/1 molar ratio) and 4.5 g of concentrated hydrochloric acid in a 21 four-hole flask equipped with a thermometer, condenser and stirrer. Preparation 1
The reaction was carried out at 10°C for 3 hours. At the end of the reaction, under reduced pressure, temperature 2
Phenol was distilled off at 00°C.

When the amount of phenol distilled out decreased, steam distillation was performed to completely remove phenol, yielding 490 g of reddish-brown polyphenol.

The softening temperature of this polyphenol is 155°C,
n=0 was 69%.

Examples 2 to 4, Comparative Examples 1 to 2 Polyphenols were obtained by changing the phenols, aromatic dialdehydes, and acid catalysts as shown in Table 1. The results are shown in Table 1.

Claims (1)

[Claims] 1) A method for producing polyphenols, which comprises reacting 1 mole of aromatic dialdehyde with 5 to 32 moles of phenol in the presence of an acid catalyst.